Pryophoric Iron Fires

At one time or another, most refineries experience spontaneous ignition of iron sulfide either on the ground or inside equipment. When this occurs inside equipment like columns, vessels, and tanks and exchangers containing residual hydrocarbons and air, the results can be devastating. Most commonly, pyrophoric iron fires occur during shutdowns when equipment and piping are opened for inspection or maintenance. Instances of fires in crude columns during turnarounds, explosions in sulfur, crude or asphalt storage tanks, overpressures in vessels, etc., due to pyrophoric iron ignition are not uncommon. Often the cause of such accidents is a lack of understanding of the phenomenon of pyrophoric iron fires. This article aims to explain the basics of pyrophoric iron fires and to provide ideas for developing safe practices for handing over equipment for inspection and maintenance.

What is Pyrophoric Iron Oxidation?
The word "pyrophoric" is derived from the Greek for "fire-bearing". According to Webster's dictionary, "pyrophoric material" means "any material igniting spontaneously or burning spontaneously in air when rubbed, scratched, or struck, e.g. finely divided metals". Iron sulfide is one such pyrophoric material that oxidizes exothermically when exposed to air. It is frequently found in solid iron sulfide scales in refinery units. It makes no difference whether these pyrophoric sulfides exist as pyrite, troilite, marcasite, or pyrrhotite. It is formed by the conversion of iron oxide (rust) into iron sulfide in an oxygen-free atmosphere where hydrogen sulfide gas is present (or where the concentration of hydrogen sulfide (H2S) exceeds that of oxygen). The individual crystals of pyrophoric iron sulfides are extremely finely divided, the result of which is that they have an enormous surface area-to-volume ratio. When the iron sulfide crystal is subsequently exposed to air, it is oxidized back to iron oxide and either free sulfur or sulfur dioxide gas is formed. This reaction between i r on sulfide and oxygen is accompanied by the generation of a considerable amount of heat. In fact, so much heat is released that individual particles of iron sulfide become incandescent. This rapid exothermic oxidation with incandescence is known as pyrophoric oxidation and it can ignite nearby flammable hydrocarbon-air mixtures.

Pryphoric Iron Fires By: Mukesh Sahdev, Associate Content Writer Presented at The Chemical Engineers’ Resource Page, www.cheresources.com

there is a greater likelihood of PIS spontaneous ignition. as shown in the equations below: The heat usually dissipates quickly unless there is an additional source of combustible material to sustain combustion. Pryphoric Iron Fires By: Mukesh Sahdev. the equipment most prone to pyrophoric combustion induced fires is the distillation columns in crude and vacuum distillation units. commonly associated with pyrophoric fires. www. It is formed by the reaction of rust or corrosion deposits with hydrogen sulfide as shown below: There is a greater likelihood of this reaction occurring when the process involves a feedstock with high sulfur content.com . The trapped combustible hydrocarbons. Associate Content Writer Presented at The Chemical Engineers’ Resource Page. to remove all the combustibles Second. Pyrophoric iron oxidation in Distillation Columns In petroleum refineries. pressure vessels.Basic chemical reactions: Iron sulfide is one of the most common substances found in refinery distillation columns. etc. that do not get adequately removed during steaming/washing often get ignited. coke. to remove or neutralize pyrophoric iron sulfide deposits The basic distillation column oil-cleanup procedure is discussed in steps below. is often mistaken for steam. The targets of these procedures should be twofold: • • First. allowing the exothermic process of rapid oxidation of the sulfides to oxides to occur. The accidents due to pyrophoric iron oxidations are entirely avoidable if safe procedures for column handover are followed.cheresources. Deposits of iron sulfide are formed from corrosion products that most readily accumulate at the trays. pump around zones. exposing the PIS to air. etc. If these pyrophoric iron sulfide (PIS) deposits are not removed properly before the columns are opened up. and structured packing. leading to fires and explosions inside the equipment. The white smoke of SO2 gas. This pyrophoric iron sulfide (PIS) lays dormant in the equipment until the equipment is shutdown and opened for service. These fires not only result in equipment damage but can also prove fatal for the personnel who are performing inspection and maintenance work inside the columns.

The condensate-soap solution can be collected and circulated through the various side cuts. chemical injection for removal of pyrophoric sulfides should be considered.com . The cold water washing is done for about 20-24 hrs.. steam should be fully closed). disposal of hydrogen sulfide gas can be a problem. The column vent and pump strainers in the side draw piping are de-blinded and steaming is started from utility connections at the bottom of the column. www. 2. water washing of the column should be started. chelating solutions are quite effective in dissolving the sulfide deposits without emitting hydrogen sulfide. This cycle of steaming and washing should be repeated several times for a total of about 15 to 20 hours. Chemical Injection for Removal and Neutralization of PIS Deposits: During the cold-water wash or after washing is over.Specially formulated.Additional chemicals can be added to the acid solution to convert or scrub the hydrogen sulfide gas. however. high pH. Acid plus hydrogen sulfide suppressant .cheresources. etc. 5. steaming is continued for about 20 to 24 hrs. as can corrosion (when the system contains more than one alloy). The various options for chemical treatment are discussed below: • Acid cleaning . Blinding: When clear water is observed at side draw pump strainers. Water flow should be stopped for 2-3 hrs and then resumed. usually via reflux lines. • • Pryphoric Iron Fires By: Mukesh Sahdev. associated pump strainers. water is sent to the column. Dilute hydrochloric acid solutions may also be used. associated piping should be isolated by installing blinds wherever isolation is possible. The water flow rate should be adjusted so that steam still comes from the vent (i. Cold Water Washing: The hot water wash should be followed by a cold water wash (i. Chelating solutions . With steam still in commission. It is effective and inexpensive. etc. The resulting iron chloride turns bright yellow. Associate Content Writer Presented at The Chemical Engineers’ Resource Page. 3. and it is drained from the column bottom. The acid dissolves sulfide scale and releases hydrogen sulfide gas. Steaming: The steaming is done after all liquid hydrocarbons have been drained from the column and associated piping.Distillation Column Oil Cleanup Procedure 1.e. acting as an indicator for removal of the iron sulfide. ensuring the column top temperature remains more than 100 °C throughout the operation. Generally. 4. Hot Water Washing: When clear steam is observed exiting the column vents.e. water should not result in condensing of all steam before it reaches the column top). Injection of a turpene-based detergent into the steam can also be considered.This procedure involves pumping in an acid with some corrosion inhibitor. The objective of steaming is to make the column and associated piping free of residual hydrocarbons. but this is an expensive application.

The colors of the fresh KMnO4 and the spent MnO2 are purple and brown respectively. dangers. the use of potassium permanganate as an oxidizer has raised serious safety and health concerns. samples are taken and checked for color. • Thus.• Oxidizing chemicals .Oxidizing chemicals convert sulfide to oxide.cheresources. In recent times. Potassium permanganate (KMnO4) has been used commonly in the past to oxidize pyrophoric sulfide. but also with foaming and exotherms during initial injection inside vessels. www. The reaction is judged complete when the solution color remains purple. Associate Content Writer Presented at The Chemical Engineers’ Resource Page. If the color of the solution becomes brown. Pryphoric Iron Fires By: Mukesh Sahdev. MnO2 is also hard on biological waste water systems. Alternative oxidation technologies are being developed with a focus on • • • • • increasing safety in application saving water eliminating odor problems minimizing wastewater problems reducing wastes The table below gives a brief overview of the various oxidizing chemicals with respect to their use. despite excellent oxidizing properties of KMnO4. additional KMnO4 is needed. limitations and advantages. Acidizing KMnO4 itself involves extremely dangerous and explosive vapors.com . • Potassium permanganate has the potential problem of very dangerous exotherms when even 2 % concentrations are exposed to many light hydrocarbons and alcohols. It takes approximately 12 hours to complete the job. many people are turning away from the drawbacks and inherent dangers in its application. At various intervals. It has been reported that numerous people have been harmed due to explosions especially during mixing. Removing the MnO 2 normally involves acidizing the equipment followed by neutralization. Generally the potassium permanganate is added to the tower during the cold water washing as a 1% solution. KMnO4 also creates large volumes of sludge waste and many customers are reporting damage to catalyst systems from MnO2 residual.

The oxidizers Zyme-Flow and Zyme-Ox are proprietary products from United Laboratories International.com or contact Mr.com. Pryphoric Iron Fires By: Mukesh Sahdev. A few of these cases are discussed below (details like the location and date of the incidents are not included).zymeflow.collins@kvaerner. the readers can visit www.com or Bcollins@ZymeFlow. www. LLC for most refinery and petrochemical decontamination applications. For more information on Zyme-Flow SM Process Technology. Bevan Collins at bevan. Case Studies: Pyrophoric Iron Fires The history of refining is replete with cases of fires and explosions due to pyrophoric iron ignitions. Associate Content Writer Presented at The Chemical Engineers’ Resource Page.com .cheresources. to give the reader an idea of the nature of pyrophoric iron fires and the lessons learned.

It was determined that the fire occurred because of the PIS ignition of residual hydrocarbons. The head cover was left in the open position. The cover was thoroughly flushed with water and kept wet. Full-face blinds should be provided wherever spool pieces are dropped. An explosion took place causing damage to the internals. The fire was immediately extinguished with water. White smoke (SO2) was also observed at the open end. After about 2 days. www. Lesson learned: Whenever exchangers in naphtha service (containing sulfur) are opened for maintenance.com . No amount of steaming can ensure full removal of PIS or residual hydrocarbons. Lessons learned : Before carrying out any maintenance activity on overhead exchangers.cheresources. fire and smoke was observed from the head cover. Air ingress occurred from this open flange. Nitrogen injection and water washing were immediately begun to quench the heat and halt the oxidation reaction inside the column. A water washing connection was made in the light vacuum gas oil (LVGO) reflux pump suction. instruction was given for removal of a 40inch spool piece in the column overhead line to facilitate overhead exchanger blinding. Associate Content Writer Presented at The Chemical Engineers’ Resource Page. Meanwhile.Pyrophoric fire/explosion inside a Vacuum column in a Crude Unit During a turnaround in the Crude Unit the vacuum column was being prepared for handover to maintenance. the exchanger areas must be properly water washed for PIS removal. the floating head cover of the naphtha stabilizer reboiler (S&T exchanger) was opened so the bundle could be pulled for cleaning. The oil was removed from the column and the column was steam purged. proper water washing and blinding must be completed. after steaming of the reboiler loop. leading to auto-ignition of pyrophoric iron sulfide inside. Pryphoric Iron Fires By: Mukesh Sahdev. Pyrophoric Fire inside the floating head cover of a Naphtha Stabilizer Reboiler During a maintenance and inspection (M&I) shutdown.

etc. Pryphoric Iron Fires By: Mukesh Sahdev. must be properly emptied and washed before allowing them to remain idle for maintenance. The heat was immediately quenched by purging with nitrogen. Upon investigation. such as naphtha.cheresources. 3. Lessons learned : Tanks in high-sulfur hydrocarbon service. it was found that PIS had ignited leading to combustion of residual naphtha in the tank.Pyrophoric Fire inside a Naphtha Tank A naphtha tank (floating head type) was emptied out for maintenance. One day. All equipment and structured packing must be properly water washed and kept wet when exposed to the atmosphere. It was left unattended for one month. Pyrophoric Fire inside a Hydrotreater Reactor During a maintenance shutdown. purging N2 must be kept opened during blinding and deblinding of the upstream and downstream flanges in exchangers. Associate Content Writer Presented at The Chemical Engineers’ Resource Page. Also. flames and smoke were observed coming from the tank. and exchangers in high-sulfur feed service must be kept properly blanketed with N2 during idle periods. The temperatures went as high as 500 oC. Tanks. columns. 2. The reactor gas loop was thoroughly nitrogen purged.com . During deblinding of the exchanger air ingress occurred to the reactor causing excessive heat build up in the reactor due to a pyrophoric iron fire. crude. The scraps and debris collected from cleaning of filters in naphtha / crude service must be kept wet and disposed of underground. a naphtha Hydrotreater reactor feed/effluent heat exchanger was to be opened.. Heavy smoke was observed from the open flanges and the reactor platform area became hot. General Precautions to Avoid Pyrophoric Iron Fires 1. such tanks should be kept under adequate nitrogen blanketing. reactors. www. Lessons learned : Whenever piping associated with a naphtha Hydrotreater reactor has to be opened.

Refineries Quarterly Safety Bulletin. Fu Huang.C. By Charles R. As the catalyst may be highly pyrophoric (containing iron sulfide.com.cheresources.E.com . NPRA Q&A Minutes. These precautions should protect against catalyst auto ignition.H. Chinese American Association of Corrosion & Materials Engineers "Formation and Oxidation of Sulfides on Pure Iron and Iron Oxides". Takeshi Inaba. In processes where catalyst handling is required (such as in Hydrotreating and fluid catalytic cracking) caution must be taken during catalyst recharge or disposal. AprilJune 1997.worlfuels. LLC . Associate Content Writer Presented at The Chemical Engineers’ Resource Page. Masatoshi Watanabe1.. www. "Methods for Removal of Iron sulphide".M. Japan “Basic Technology of Zyme-Flow Process”. International Technical Director. the used catalyst may be emptied into drums for later shipment to a regenerator or a disposal site. References "Pyrophoric Materials Handbook. the possibility exists for iron sulfide fires. If the spent catalyst is warm and contacts oxygen.. Tohoku University.4. iron sulfide will ignite spontaneously and the ensuing reaction may generate enough heat to ignite carbon deposited on the catalyst. Bevan Collins. Edited By Jeff Schmitt "Pyrophoric Fires and Column Shutdown". etc. Department of Metallurgy. Sendai 980-8579.). Graduate School of Engineering. www. cooled to about 50 o C and wetted with water to prevent it from igniting vapors. When unloading any spent coked catalyst. Once cooled. Therefore catalyst must be stripped of all hydrocarbons.com TECHNICAL BULLETIN: Safe Handling of CRITERION Hydrotreating Catalysts www. United Laboratories. Flammable Metals and Materials". C. P. The drum and liner should first be filled with inert gas. The liner should be tied off and a small chunk of dry ice placed inside the drum before sealing. and Yasutaka Iguchi. Schmitt. 1999 Session I Pryphoric Iron Fires By: Mukesh Sahdev. which is then displaced by the catalyst. it should be dumped into drums containing an internal liner for shipment. Mr.zymeflow. Minoru Sakuma.